CN102803385B - Polyamide resin composition and method for producing polyamide resin composition - Google Patents
Polyamide resin composition and method for producing polyamide resin composition Download PDFInfo
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- CN102803385B CN102803385B CN201180014366.9A CN201180014366A CN102803385B CN 102803385 B CN102803385 B CN 102803385B CN 201180014366 A CN201180014366 A CN 201180014366A CN 102803385 B CN102803385 B CN 102803385B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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Abstract
Disclosed is a polyamide resin composition which is characterized by containing 0.01-50 parts by mass of cellulose fibers having an average fiber diameter of 10 [mu]m or less per 100 parts by mass of a polyamide resin. Also disclosed is a method for producing a polyamide resin composition, which is characterized in that cellulose fibers having an average fiber diameter of 10 [mu]m or less and containing water and carrying out a polymerization reaction of a monomer that constitutes a polyamide resin.
Description
Technical field
The present invention relates to mechanical characteristics, the manufacturing process of Amilan polyamide resin composition that thermotolerance improves and this resin combination.
Background technology
Utilize the inorganic filler such as glass fibre, carbon fiber, talcum, clay strengthening polyamide resin and the resin combination that obtains is well-known.But there are the following problems for these strengthening materials, if that is, do not coordinated in a large number, cannot improve mechanical characteristics, this problem of thermotolerance, the quality of the resin combination obtained because proportion is high becomes large this problem.
In addition, when adopting glass fibre, carbon fiber etc. as strengthening material, the formed body formed by the resin combination obtained has warpage and becomes large this problem.In addition, when adopting talcum, clay etc. as strengthening material, when the resin combination that obtains is discarded, these strengthening materials remain as incineration residue, therefore, bury process underground and can have and semi-permanently residue in this problem in ground in soil.
Use Mierocrystalline cellulose as the strengthening material of resin material in recent years.Fiber have the bacteria cellulose etc. of the Mierocrystalline cellulose obtained by trees, the Mierocrystalline cellulose obtained by non-timber resources such as rice, cotton, mestha, fiber crops, microorganisms producing, and Mierocrystalline cellulose exists on earth very in large quantities.Cellulosic mechanical characteristics is excellent, by making, containing Mierocrystalline cellulose in resin, to expect the effect making the characteristic of resin combination improve.
As making containing cellulosic method in thermoplastic resin, normally by the method for resin and Mierocrystalline cellulose melting mixing.But when adopting the method, Mierocrystalline cellulose is mixed in resin with the state of cohesion, can not obtain the homodisperse resin combination of Mierocrystalline cellulose.Therefore, the characteristic of resin combination can not be made fully to improve.
Such as, Patent Document 1 discloses the matrix material containing cellulosic pulp fibers in thermoplastics, also describe polyamide resin as thermoplastics.In the invention, also describing to make cellulosic pulp fibers easily mix with polymer materials, utilizing rotary cutter etc. to make granular.But describe in patent documentation 1, if make fiber length shorten owing to making granular, then the stiffening force produced by adding cellulosic pulp fibers reduces, and the average length therefore describing cellulosic pulp fibers is preferably 0.1 ~ 6mm.
And then, in the invention that citing document 1 is recorded, cellulosic pulp fibers is blended in thermoplastics in a large number, adds cellulosic pulp fibers in an embodiment in a large number and reach 30 quality %.
So, in the invention that citing document 1 is recorded, when being mixed with polymer materials by cellulosic pulp fibers, after making cellulosic pulp fibers drying, carry out melting mixing.
In sum, in the invention that citing document 1 is recorded, do not solve the problem of cellulosic pulp fibers cohesion, and, addition due to cellulosic pulp fibers is a large amount of, if be therefore the temperature of 230 ~ 240 DEG C when injection molding, then also can produce the coloring problem caused by cellulose decomposition.
In addition, in patent documentation 2, describe the thermoplastics containing cellulosic fibre 0.01 ~ 20 weight part in plastics 100 weight part.And describe cellulosic fibre and be preferably viscose fiber and there is the staple length of 50 μm ~ 5mm or the Fibre diameter of 1 ~ 500 μm.In the invention that patent documentation 2 is recorded, compared with the invention recorded with patent documentation 1, the content of cellulosic fibre is a small amount of, but the fiber of cellulosic fibre is long, Fibre diameter is large, and, as the method made it containing cellulosic fibre, illustrate only the method for melting mixing.
Therefore, in the invention that patent documentation 2 is recorded, the problem of cellulosic fibre as above cohesion is not solved yet.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2002-527536 publication
Patent documentation 2: Japanese Kohyo 9-505329 publication
Summary of the invention
The present invention is the technical scheme solved the problem, and object is to be provided in cellulosic fibre in polyamide resin and does not condense and disperse equably and the manufacturing process of the Amilan polyamide resin composition that improves of mechanical characteristics, thermotolerance and this resin combination.
The present inventor etc. further investigate repeatedly in order to solve above-mentioned problem, and result completes the present invention.
That is, purport of the present invention is as follows.
(1) Amilan polyamide resin composition, is characterized in that, relative to polyamide resin 100 mass parts, is cellulosic fibre 0.01 ~ 50 mass parts of less than 10 μm containing fiber diameter.
(2) Amilan polyamide resin composition Gen Ju (1), its by be less than 10 μm in fiber diameter and under the existence of the cellulosic fibre of state containing water, the polyreaction of monomer of carrying out forming polyamide resin obtains.
(3) Amilan polyamide resin composition Gen Ju (1), wherein, heat-drawn wire during load 1.8MPa is more than 50 DEG C.
(4) Amilan polyamide resin composition Gen Ju (1), wherein, the linear expansivity (calculate the mean value in 20 ~ 150 DEG C of regions and obtain) in MD direction is 120 × 10
-6(1/ DEG C) below.
(5) Amilan polyamide resin composition Gen Ju (1), wherein, heat-drawn wire during load 1.8MPa is more than 50 DEG C, and the linear expansivity (calculate the mean value in 20 ~ 150 DEG C of regions and obtain) in MD direction is 120 × 10
-6(1/ DEG C) below.
(6) Amilan polyamide resin composition Gen Ju (1), wherein, heat-drawn wire during load 1.8MPa is more than 65 DEG C.
(7) Amilan polyamide resin composition Gen Ju (1), wherein, the linear expansivity (calculate the mean value in 20 ~ 150 DEG C of regions and obtain) in MD direction is 80 × 10
-6(1/ DEG C) below.
(8) Amilan polyamide resin composition Gen Ju (1), wherein, heat-drawn wire during load 1.8MPa is more than 65 DEG C, and the linear expansivity (calculate the mean value in 20 ~ 150 DEG C of regions and obtain) in MD direction is 80 × 10
-6(1/ DEG C) below.
(9) according to the Amilan polyamide resin composition according to any one of (1) ~ (5), wherein, polyamide resin is nylon 11 or nylon 12.
(10) according to (1), (2), Amilan polyamide resin composition according to any one of (6) ~ (8), wherein, polyamide resin is nylon 6 or nylon66 fiber.
(11) a kind of manufacturing process of Amilan polyamide resin composition, it is the method for the manufacture of the Amilan polyamide resin composition according to any one of above-mentioned (1) ~ (10), it is characterized in that, fiber diameter be less than 10 μm and the cellulosic fibre of state containing water existence under, carry out the polyreaction of monomer forming polyamide resin.
Amilan polyamide resin composition of the present invention contains the cellulosic fibre that fiber diameter is less than 10 μm, and in resin combination, this cellulosic fibre does not condense dispersed, and therefore, the mechanical characteristics such as intensity, linear expansivity, thermotolerance improve.Therefore, Amilan polyamide resin composition of the present invention can adopt the methods of forming such as injection molding, extrusion moulding, foaming to obtain various formed body, may be used for various purposes.
And adopt the manufacturing process of Amilan polyamide resin composition of the present invention, cellulosic fibre is contained in polyamide resin with can not keeping state of aggregation, therefore, the dispersed Amilan polyamide resin composition of the present invention having cellulosic fibre can be obtained.So, even if the comparision contents of cellulosic fibre is a small amount of, the mechanical characteristics of Amilan polyamide resin composition, thermotolerance also can be made to improve.
Accompanying drawing explanation
Fig. 1: the electron micrograph in the cross section of the resin combination obtained in embodiment 9.
Fig. 2: the electron micrograph in the cross section of the resin combination obtained in comparative example 10.
Embodiment
Below, the present invention is described in detail.
The polyamide resin used in the present invention is the polymkeric substance with the amido linkage formed by amino acid, lactan or diamines and dicarboxylic acid.
As the example of the monomer of this polyamide resin of formation, as amino acid, 6-aminocaprolc acid, 11-amino undecanoic acid, 12 amino dodecanoic acid, paraaminomethyl benzoic acid etc. can be enumerated.
As lactan, ε-caprolactam, omega-lauric lactam etc. can be enumerated.
As diamines, tetramethylene-diamine, hexamethylene-diamine, nonamethylene diamine, decamethylene diamine, 11 methylene diamine, ten dimethylene diamines, 2,2,4-/2,4,4-trimethylhexamethylenediamines, 5-methyl nonamethylene diamine, 2,4-can be enumerated
-dimethyl-octa diamines, m-xylene diamine, p-Xylol diamines, 1,3-two (aminomethyl) hexanaphthene, 1-amino-3-amino methyl-3,5,5-trimethyl-cyclohexane, 3, two (aminomethyl) tristane of 8-, two (4-aminocyclohexyl) methane, two (3-methyl-4-aminocyclohexyl) methane, 2,2-two (4-aminocyclohexyl) propane, two (aminopropyl) piperazine, aminoethylpiperazine etc.
As dicarboxylic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid, terephthalic acid, m-phthalic acid, naphthalic acid, 2-chlorine terephthalic acid, 2-methylterephthalic acid, oreinol dioctyl phthalate, 5-sodium sulfo isophthalate, six hydrogen terephthalic acids, six hydrogen m-phthalic acids, diglycollic acid etc. can be enumerated.
More specifically, as the polyamide resin used in the present invention, polycaproamide (nylon 6) can be enumerated, nylon 46 (nylon 46), polyhexamethylene adipamide (nylon66 fiber), polyhexamethylene sebacamide (NYLON610), nylon 612 (nylon 612), poly hexamethylene adipamide undecane diamines (nylon 11 6), nylon 11 (nylon 11), poly-lauramide (nylon 12), poly-paraphenylene terephthalamide's trimethylhexane diamine (nylon TMHT), poly-hexamethylene terephthalamide (nylon 6T), poly-6I hexamethylene isoterephalamide (nylon 6I), poly-hexamethylene terephthalamide/6I hexamethylene isoterephalamide (nylon 6T/6I), poly-two (4-aminocyclohexyl) methane dodecane acid amides (nylon PACM12), poly-two (3-methyl-4-aminocyclohexyl) methane dodecane acid amides (nylon dimethyl PACM12), poly-meta-xylylene adipamide (nylon MXD 6), poly-paraphenylene terephthalamide's nonamethylene diamine (nylon 9 T), poly-paraphenylene terephthalamide's decamethylene diamine (nylon 10T), poly-paraphenylene terephthalamide's undecane diamines (nylon 11 T), poly-six hydrogen paraphenylene terephthalamide undecane diamines (nylon 11 T (H)) also can be their multipolymers, mixture.Wherein particularly preferred polyamide resin is nylon 6, nylon66 fiber, nylon 11, nylon 12 and their multipolymer, mixture.
Amilan polyamide resin composition of the present invention contains polyamide resin as above and cellulosic fibre.As the cellulosic fibre used in the present invention, comprise the cellulosic fibre from timber, rice, cotton, fiber crops, mestha etc., in addition also comprise the Mierocrystalline cellulose from biology such as bacteria cellulose, Mongolian oak bucket Mierocrystalline cellulose, Ascidian Mierocrystalline cellulose.Comprise regenerated cellulose, derivatived cellulose etc. in addition.
Amilan polyamide resin composition of the present invention is by making the mechanical characteristics such as intensity, linear expansivity, thermotolerance improve containing cellulosic fibre.Make the mechanical characteristics of resin combination, thermotolerance is when fully improving, need to make cellulosic fibre not condense and be evenly dispersed in resin.Therefore, cellulosic fibre is important for the affinity of the dispersiveness of polyamide resin, polyamide resin and cellulosic fibre.In addition, in order to play the character of hydroxyl that cellulosic fibre has etc. as much as possible, the surface-area of increased fiber cellulose fiber is important.Therefore, the cellulosic fibre using miniaturization is as far as possible needed.
Therefore, in the present invention, as cellulosic fibre, need to use fiber diameter to be the cellulosic fibre of less than 10 μm, wherein, fiber diameter is preferably below 500nm, more preferably below 300nm, is more preferably below 100nm.The cellulosic fibre of fiber diameter more than 10 μm can not the surface-area of increased fiber cellulose fiber, is difficult to improve for polyamide resin, the dispersiveness, the affinity that form the monomer of polyamide resin.The lower limit of fiber diameter is not particularly limited, if but the productivity of consideration cellulosic fibre, be then preferably more than 4nm.
As the cellulosic fibre (following, be sometimes referred to as cellulosic fibre (A)) that this fiber diameter is less than 10 μm, preferably by the cellulosic fibre tearing cellulosic fibre and come primitive fiber.As the device of primitive fiber, the various shredding units such as ball mill, stone mortar pulverizer, high-pressure homogenizer, mixing tank can be used.As cellulosic fibre (A), as commercially available product, such as, can use " CELISH " of Daicel Finechem Inc..
In addition, as cellulosic fibre (A), the aggregation of the cellulosic fibre produced as broken silk in the manufacturing process of the fibre product employing cellulosic fibre also can be used in.The manufacturing process of so-called fibre product, when can enumerate weaving, the time of weaving cotton cloth, non-woven fabrics when manufacturing, other fibre product add man-hour etc.The aggregation of these cellulosic fibres is becoming broken silk due to cellulosic fibre after these operations, therefore, and cellulosic fibre miniaturization.
In addition, as cellulosic fibre (A), the bacteria cellulose that bacterium produces can also be used, such as, can use the bacteria cellulose produced as producing bacterium using the acetic acid mattress of acetobacter.Because the cellulose molecular chain of plant cellulose collects bunchy, therefore, bunchy forms very thin primitive fiber, and the band shape of the Mierocrystalline cellulose produced by acetic bacteria originally wide 20 ~ 50nm, compared with plant cellulose, is formed superfine netted.
In addition, after making cellulosic fibre be oxidized under also can being used in the existence of N-oxyradical compound, by obtaining through washing, the fine operation of physical solution, the cellulosic fibre of miniaturization is as cellulosic fibre (A).
As N-oxyradical compound, have various, 2,2,6, the 6-tetramethyl piperidine-1-oxyradicals (below write TEMPO) etc. of preference as shown in such as Cellulose (1998) 5,153-164.Such compound is added in reacting solution with the scope of catalytic amount.
In this aqueous solution, add clorox, Textone as co-oxidants, add alkali bromide metal, make reaction carry out thus.Adding the basic cpds such as aqueous sodium hydroxide solution remains near 10 by pH, continues reaction until cannot observe the change of pH.Temperature of reaction can be room temperature.The N-oxyradical compound remained in system is removed after preferred reaction.Washing can adopt the various methods such as filtration, centrifugation.
Then, can by utilizing various shredding unit as above, obtaining the cellulosic fibre (A) of miniaturization through the fine operation of physical solution.
In the present invention, the measuring method of the fiber diameter of the cellulosic fibre contained in resin combination is as follows.Utilize cryoultramicrotome to cut the section that thickness is 100nm from resin combination (or the formed body formed by resin combination), use OsO
4after (perosmic anhydride) implements section statining, transmission electron microscope (NEC Inc. JEM-1230) is used to observe.The length in the direction vertical with the length direction of cellulosic fibre (ultimate fibre) is measured by electron microscope image.Now, using length maximum among the length of vertical direction as Fibre diameter.Similarly measure the Fibre diameter of 10 cellulosic fibres (ultimate fibre), calculate the mean value of 10 as fiber diameter.
Should illustrate, for the cellulosic fibre that the Fibre diameter of cellulosic fibre is large, slicing machine is utilized to be cut into the section of 10 μm, or under the state of being kept intact by resin combination (or the formed body formed by resin combination), utilize stereoscopic microscope (OLYMPUS SZ-40) to observe, measure Fibre diameter as described above by the image obtained, try to achieve fiber diameter.
In addition, the length of the cellulosic fibre contained in resin combination of the present invention can be tried to achieve when such as measuring fiber diameter above-mentioned institute, is called the length of the length direction of the cellulosic fibre (ultimate fibre) in electron microscope image.Then, measure the length of 10 cellulosic fibres (ultimate fibre) in the same manner as Fibre diameter, the mean value calculating 10 is long as average fiber.
Cellulosic fibre of the present invention is preferably more than 10 as above-mentioned fiber diameter and the aspect ratio (average fiber length/fiber diameter) of the ratio of average fiber length, particularly preferably more than 50, further preferably more than 100.Be more than 10 by aspect ratio, the cellulosic fibre that the mechanical characteristics that can form Amilan polyamide resin composition easily improves, intensity is higher, linear expansivity is low.
Should illustrate, Amilan polyamide resin composition of the present invention adopts manufacturing process of the present invention as described later to obtain, even if the aspect ratio of cellulosic fibre (A) is more than 100 thus, also can be evenly dispersed in resin.
And, the content of the cellulosic fibre (A) in Amilan polyamide resin composition of the present invention is necessary for 0.01 ~ 50 mass parts relative to polyamide resin 100 mass parts, wherein be preferably 0.05 ~ 30 mass parts, more preferably 0.1 ~ 20 mass parts, is more preferably 0.1 ~ 10 mass parts.The content of cellulosic fibre (A) relative to polyamide resin 100 mass parts lower than 0.01 mass parts time, the effect containing cellulosic fibre (A) as above can not be played, namely improve the effect of mechanical characteristics, thermotolerance.On the other hand, the content of cellulosic fibre (A) relative to polyamide resin 100 mass parts more than 50 mass parts time, become and be difficult to make in resin combination containing cellulosic fibre (A), if or the resin combination obtained is heat-treated with high temperature when injection molding etc. is shaping, then produce variable color.
Amilan polyamide resin composition of the present invention is obtained by adopting manufacturing process of the present invention as described later, even if the content of cellulosic fibre (A) is a small amount of, it is also evenly dispersed in polyamide resin, therefore, Amilan polyamide resin composition obtains the raising effect of sufficient mechanical characteristics, thermotolerance.Namely, even if the content of cellulosic fibre (A) is the scope of 0.01 ~ 10 mass parts relative to polyamide resin 100 mass parts, Amilan polyamide resin composition also can become that intensity is high, linear expansivity is low, mechanical characteristics is excellent and the also excellent composition of thermotolerance.
Amilan polyamide resin composition preferred number average molecular weight of the present invention containing polyamide resin as above and cellulosic fibre (A) is 10,000 ~ 100,000.Number-average molecular weight lower than 10,000 time, the mechanical characteristics of resin combination reduces, thus not preferred.On the other hand, when number-average molecular weight is more than 100,000, the formability of resin combination reduces rapidly, thus not preferred.Should illustrate, number-average molecular weight is the value utilizing the gel possessing differential refraction rate detector to soak into chromatogram (GPC) device, being tried to achieve by being converted into PMMA at 40 DEG C as elutriant by hexafluoroisopropanol.
The affinity of cellulosic fibre and water is very high, and fiber diameter is more little more can keep good dispersion state to water.In addition, if dehydration, then cellulosic fibre condenses securely each other by hydrogen bond, once cohesion, is then difficult to obtain the dispersion state same with before cohesion.Especially the fiber diameter of cellulosic fibre becomes less, and this trend becomes more obvious.
Therefore, cellulosic fibre preferably under containing the state of water with polyamide resin Composite.
So, as the manufacturing process of Amilan polyamide resin composition of the present invention, preferred employing following methods: when obtaining polyamide resin by polyreaction, mixes the monomer forming polyamide resin with the aqueous dispersions of cellulosic fibre (A), carries out polyreaction.Namely, manufacturing process of the present invention is following methods: when polyamide resin is polymerized, and the cellulosic fibre of the state containing water is existed, carries out polyreaction, obtains the resin combination containing cellulosic fibre (A) thus.
By adopting such manufacturing process of the present invention, cellulosic fibre (A) can be obtained and do not condense and the Amilan polyamide resin composition disperseed equably, the resin combination that especially mechanical characteristics and thermotolerance improve can be made.
The excellent heat resistance of Amilan polyamide resin composition of the present invention.As the index representing thermotolerance, it is heat-drawn wire.Heat-drawn wire during the preferred load 1.8MPa of Amilan polyamide resin composition of the present invention is more than 50 DEG C, particularly preferably more than 60 DEG C, preferably more than 70 DEG C further.If heat-drawn wire during load 1.8MPa is lower than 50 DEG C, then not there is enough thermotolerances, become and be difficult to use in various purposes.
When using nylon 6, nylon66 fiber as polyamide resin, heat-drawn wire during load 1.8MPa is preferably more than 65 DEG C, particularly preferably more than 70 DEG C, preferably more than 80 DEG C further.In addition, when using nylon 11, nylon 12, be preferably more than 50 DEG C, particularly preferably more than 55 DEG C.
In addition, heat-drawn wire during the preferred load 0.45MPa of Amilan polyamide resin composition of the present invention is more than 148 DEG C, particularly preferably more than 155 DEG C, preferably more than 180 DEG C further.If heat-drawn wire during load 0.45MPa is lower than 148 DEG C, then not there is enough thermotolerances, become and be difficult to use in various purposes.
When using nylon 6, nylon66 fiber as polyamide resin, heat-drawn wire during load 0.45MPa is preferably more than 180 DEG C, particularly preferably more than 190 DEG C.In addition, when using nylon 11, nylon 12, be preferably more than 148 DEG C, particularly preferably more than 150 DEG C.
Should illustrate, the heat-drawn wire in the present invention is the value adopting the test film identical with the test film made when mensuration flexural strength described later, bending elastic modulus, measure based on ASTM D648.Now, measure under load 1.8MPa and 0.45MPa.
The mechanical characteristics of Amilan polyamide resin composition of the present invention is also excellent.As the index representing mechanical characteristics, there are linear expansivity, intensity.
The linear expansivity in the preferred MD direction of Amilan polyamide resin composition of the present invention is 120 × 10
-6(1/ DEG C) below, is particularly preferably 100 × 10
-6(1/ DEG C) below, more preferably 80 × 10
-6(1/ DEG C) below.If the linear expansivity in MD direction is more than 120 × 10
-6(1/ DEG C), then easily form the poor composition of dimensional stability, be difficult to use in various purposes.
When using nylon 6, nylon66 fiber as polyamide resin, the linear expansivity in MD direction is preferably 80 × 10
-6(1/ DEG C) below, especially preferably 70 × 10
-6(1/ DEG C) below, more preferably 50 × 10
-6(1/ DEG C) below.When using nylon 11, nylon 12 as polyamide resin, the linear expansivity in MD direction is preferably 120 × 10
-6(1/ DEG C) below, particularly preferably 110 × 10
-6(1/ DEG C) below.
Should illustrate, the linear expansivity in the present invention is the value adopting the test film identical with the test film made when mensuration flexural strength described later, bending elastic modulus, measure based on JIS K7197, calculates the mean value in 20 ~ 150 DEG C of regions.In addition, the flow direction of resin time shaping is MD direction, and the direction vertical with flowing is TD direction.
The preferred flexural strength of Amilan polyamide resin composition of the present invention is more than 65MPa, particularly preferably more than 70MPa, further preferred more than 100MPa.In addition, tensile yield strength is preferably more than 40MPa, particularly preferably more than 45MPa, further preferred more than 70MPa.
If flexural strength lower than 40MPa lower than 65MPa or tensile yield strength, does not then have enough intensity, becomes and be difficult to use in various purposes.
When using nylon 6, nylon66 fiber as polyamide resin, the flexural strength of Amilan polyamide resin composition of the present invention is preferably more than 120MPa, particularly preferably more than 130MPa, more preferably more than 140MPa.Tensile yield strength is preferably more than 70MPa, particularly preferably more than 75MPa, more preferably more than 80MPa.
When using nylon 11, nylon 12 as polyamide resin, flexural strength is preferably more than 65MPa, particularly preferably more than 70MPa.Tensile yield strength is preferably more than 40MPa, particularly preferably more than 45MPa.
And then the bending elastic modulus of Amilan polyamide resin composition of the present invention is preferably more than 1.8GPa, particularly preferably more than 2.5GPa, more preferably more than 3.0GPa.And modulus in tension is preferably more than 1.4GPa, particularly preferably more than 2.0GPa, more preferably more than 2.2GPa.
If bending elastic modulus lower than 1.8GPa or modulus in tension lower than 1.4GPa, then lack flexibility, rigidity become too strong, therefore, even if flexural strength, tensile yield strength are in above-mentioned scope, also versatility can be lacked, thus not preferred in practical application.
When using nylon 6, nylon66 fiber as polyamide resin, the bending elastic modulus of Amilan polyamide resin composition of the present invention is preferably more than 2.5GPa, particularly preferably more than 3.0GPa, more preferably more than 3.3GPa.Modulus in tension is preferably more than 2.0GPa, particularly preferably more than 2.2GPa, more preferably more than 2.4GPa.
When using nylon 11, nylon 12 as polyamide resin, bending elastic modulus is preferably more than 1.8GPa, particularly preferably more than 2.0GPa.Modulus in tension is preferably more than 1.4GPa, more preferably more than 1.5GPa.
Should illustrate, the flexural strength in the present invention, tensile yield strength, bending elastic modulus, modulus in tension adopt by injection molding condition as described below obtain test film, based on ASTM D790, carry out measuring obtaining at 23 DEG C.
(injection molding condition)
To Amilan polyamide resin composition, adopt injection moulding machine (Toshiba Machine Co. Ltd's system, IS-80G type), utilize 1/8 of ASTM specification inch 3 pliability test sheet moulds to carry out shaping, obtain the test film of length x width x thickness=127mm (5 inches) × 12.7mm (1/2 inch) × 3.2mm (1/8 inch).
Then, the manufacturing process of Amilan polyamide resin composition of the present invention is described.
The manufacturing process of Amilan polyamide resin composition of the present invention is: under fiber diameter is less than 10 μm and contains the existence of the cellulosic fibre of the state of water, carry out the polyreaction of the monomer forming polyamide resin, such as, the aqueous dispersions being the cellulosic fibre of less than 10 μm by the monomer of formation polyamide resin and fiber diameter mixes, and carries out polyreaction.And this fiber diameter is that the cellulosic fibre of less than 10 μm is dispersed in water and obtains by the aqueous dispersions of the cellulosic fibre in manufacturing process of the present invention, and the content of the cellulosic fibre in aqueous dispersions is preferably 0.01 ~ 50 quality %.Such aqueous dispersions can obtain by utilizing mixing tank etc. to stir Purified Water and cellulosic fibre.
So, the aqueous dispersions of cellulosic fibre is mixed with the monomer forming polyamide resin, utilizes mixing tank etc. to stir, make uniform dispersion liquid thus.Then, heating dispersion liquid, is warmed up to 150 ~ 270 DEG C and stirs, carrying out polyreaction thus.Now, by discharging water vapor lentamente when heating dispersion liquid, the moisture in the aqueous dispersions of cellulosic fibre can be discharged.Should illustrate, when above-mentioned polymerizing polyamide, the catalyzer such as phosphoric acid, phosphorous acid can be added as required.And, after polyreaction completes, cut off after preferably the resin combination obtained being taken out and make particle.
In addition, when using bacteria cellulose as cellulosic fibre, as the aqueous dispersions of cellulosic fibre, bacteria cellulose also can be used to be dipped in and to carry out solvent exchange in Purified Water and the solution that obtains.During the aqueous dispersions obtained using the solvent exchange of bacteria cellulose, after preferred solvent displacement, after adjusting to the concentration of regulation, mixing with the monomer forming polyamide resin, carrying out polyreaction as described above.
Like this, adopt manufacturing process of the present invention, use fiber diameter is the cellulosic fibre of less than 10 μm, and keeps the state of aqueous dispersions that cellulosic fibre is supplied polyreaction, supplies polyreaction thus under the state of favorable dispersity.And then, monomer in the supply cellulosic fibre of polyreaction and polyreaction, aqueous phase mutual effect, and stir under temperature condition as above, can obtain thus dispersed to improve, resin combination that fiber does not condense each other, fiber diameter is little cellulosic fibre disperses well.Like this, adopt manufacturing process of the present invention, the dispersiveness of cellulosic fibre improves, therefore, compared with the fiber diameter at the cellulosic fibre added before polyreaction, the cellulosic fibre fiber diameter contained in resin combination after polyreaction completes, fiber are long can be less.
And, adopt manufacturing process of the present invention not need the operation of dry cellulose fibres, manufacture to the operation can dispersed without generation fine cellulose fiber, therefore, workability can obtain Amilan polyamide resin composition well.And, do not need to make monomer and Mierocrystalline cellulose disperse equably and water be replaced as organic solvent, therefore, the discharge of chemical substance while treatability excellence, can be suppressed in manufacturing process.
Should illustrate, use in manufacturing process of the present invention, before polyreaction, the measuring method of the fiber diameter of cellulosic fibre is as follows.First, utilize electric field radioactive scanning electron microscope (Inc. of Hitachi S-4000) to observe and carry out cryodesiccated cellulosic fibre as required.By the length in electron microscope (SEM) the determining image direction vertical with cellulosic fibre (ultimate fibre) length direction.Now, using the maximum value among the length of vertical direction as Fibre diameter.Similarly measure the Fibre diameter of 10 cellulosic fibres (ultimate fibre), calculate the value of 10 mean values as fiber diameter.
In Amilan polyamide resin composition of the present invention, as long as damage its characteristic not significantly, then can contain pigment, thermo-stabilizer, antioxidant, weather resisting agent, softening agent, lubricant, releasing agent, static inhibitor, shock-resistant dose, fire retardant, compatilizer etc.
In addition, in Amilan polyamide resin composition of the present invention, as long as damage its characteristic not significantly, then can containing other polymkeric substance except polyamide resin.As other polymkeric substance, such as, can enumerate polyolefine, polyester, polycarbonate, polystyrene, poly-(methyl) methyl acrylate, poly-(acrylonitrile-butadiene-styrene (ABS)) multipolymer, liquid crystalline polymers, polyacetal etc.
Should illustrate, Amilan polyamide resin composition of the present invention can adopt the forming methods such as injection molding, blow molding, extrusion moulding, foaming to make various formed body.That is, can make the film of the formed body of injection molding or extrusion moulding, sheet material and the formed body processed by these films, sheet material or blow molding ducted body and the formed body processed by this ducted body, carry out melt-spinning and the fiber etc. obtained.
As the concrete example of these formed bodys, the electrified goods resin component of computer frame parts and framework, mobile telephone frame part and framework, other OA machine frame parts, junctor class etc. can be enumerated; With automobile resin components such as the panels around collision bumper, dashboard, controlling box, ornament, door trim, ceiling, base plate, engine for representative, the agriculture equipment such as container, cultivating container, agricultural machine resin component; The aquatic products business resin components such as buoy, fishery technology container; Tableware, the food product containers such as dish, cup, spoon; The medical resin components such as syringe, drop container; The house civil construction material resin components such as drainage material, fence, containing box, engineering switchboard; The green material application resin components such as flower bed brick, flowerpot; The amusement and leisure groceries resin components such as insulation can, fan, toy; The stationery resin components such as ballpoint pen, ruler, clip; The cloth that braided fiber obtains, non-woven fabrics etc.
Embodiment
Below, the present invention is specifically described further by embodiment.Should illustrate, the assay method of the various characteristic values in embodiment is as follows.
(bending elastic modulus, flexural strength)
The Amilan polyamide resin composition (particle) obtained is used to adopt aforesaid method to measure.
(modulus in tension, tensile yield strength)
The Amilan polyamide resin composition (particle) obtained is used to adopt aforesaid method to measure.
(heat-drawn wire (HDT))
The Amilan polyamide resin composition (particle) obtained is used to adopt aforesaid method to measure.
(linear expansivity)
The Amilan polyamide resin composition (particle) obtained is used to adopt aforesaid method to measure.
(fiber diameter of cellulosic fibre)
In the Amilan polyamide resin composition obtained cellulosic fibre fiber diameter, supply polyreaction polyreaction before cellulosic fibre fiber diameter adopt aforesaid method measure, calculate.
Embodiment 1
As the aqueous dispersions of cellulosic fibre, use CELISH KY100G (Daicel Finechem Inc.: the aqueous dispersions containing 10 quality % fiber diameter being the cellulosic fibre of 125nm), adding Purified Water wherein utilizes mixing tank to stir, and the content preparing cellulosic fibre is the aqueous dispersions of 3 quality %.
With mixing tank, aqueous dispersions 170 mass parts of this cellulosic fibre, ε-caprolactam 216 mass parts, hexosamine 44 mass parts and phosphorous acid 0.59 mass parts are stirred, are mixed to and become uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 240 DEG C in heating way, stir 1 hour at 240 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is barrel temperature is 260 DEG C, die temperature is 80 DEG C.
Embodiment 2
The content preparing cellulosic fibre is similarly to Example 1 the aqueous dispersions of 3 quality %, aqueous dispersions 70 mass parts of this cellulosic fibre and ε-caprolactam 100 mass parts is stirred, is mixed to and becomes uniform dispersion liquid further with mixing tank.Then, while stir this mixed dispersion liquid limit to be heated to 240 DEG C, water vapor is released lentamente, simultaneously from 0kgf/cm
2boost to 7kgf/cm
2pressure.Then relief pressure is to normal atmosphere, carries out polyreaction 1 hour at 240 DEG C.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Embodiment 3
The content preparing cellulosic fibre is similarly to Example 1 the aqueous dispersions of 3 quality %, aqueous dispersions 70 mass parts of this cellulosic fibre and nylon salt 100 mass parts is stirred with mixing tank, is mixed to and becomes uniform dispersion liquid.Then, while stir this mixed dispersion liquid limit at 230 DEG C, to be heated to interior pressure be 15kgf/cm
2.After reaching this pressure, release water vapor lentamente, continue heating simultaneously and keep this pressure.Reaching the time point of 280 DEG C, relief pressure, to normal pressure, carries out polymerization 1 hour further.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is barrel temperature is 290 DEG C, die temperature is 80 DEG C.
Embodiment 4
The content preparing cellulosic fibre is similarly to Example 1 the aqueous dispersions of 1.3 quality %.With mixing tank, aqueous dispersions 210 mass parts of this cellulosic fibre, amino undecanoic acid 140 mass parts and phosphorous acid 0.14 mass parts are stirred, are mixed to and become uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 200 DEG C in the way of heating, stir 1 hour at 240 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.The particle obtained directly supplies the shaping of test film.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is barrel temperature is 210 DEG C, die temperature is 80 DEG C.
Embodiment 5
The content preparing cellulosic fibre is similarly to Example 1 the aqueous dispersions of 3 quality %, aqueous dispersions 70 mass parts of this cellulosic fibre and 12 amino dodecanoic acid 100 mass parts is stirred with mixing tank, is mixed to and becomes uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 200 DEG C in the way of heating, stir 1 hour at 230 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.The particle obtained directly supplies the shaping of test film.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is barrel temperature is 210 DEG C, die temperature is 80 DEG C.
Embodiment 6
As the aqueous dispersions of cellulosic fibre, use CELISH KY100S (Daicel Finechem Inc.: the aqueous dispersions containing 25 quality % fiber diameter being the cellulosic fibre of 140nm).With mixing tank, aqueous dispersions 98 mass parts of this cellulosic fibre, ε-caprolactam 216 mass parts, hexosamine 44 mass parts, phosphorous acid 0.59 mass parts and Purified Water 157 mass parts are stirred, are mixed to and become uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 240 DEG C in the way of heating, stir 1 hour at 240 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Embodiment 7
As the aqueous dispersions of cellulosic fibre, use CELISH KY100S (Daicel Finechem Inc.: the aqueous dispersions containing 25 quality % fiber diameter being the cellulosic fibre of 140nm).With mixing tank, aqueous dispersions 160 mass parts of this cellulosic fibre, ε-caprolactam 170 mass parts, hexosamine 30 mass parts, phosphorous acid 0.35 mass parts and Purified Water 150 mass parts are stirred, are mixed to and become uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 240 DEG C in the way of heating, stir 1 hour at 240 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Production Example 1: the manufacture of bacteria cellulose
The substratum 50mL be made up of 0.5 quality % glucose, 0.5 quality % polyprotein peptone, 0.5 quality % yeast extract, 0.1 quality % magnesium sulfate 7 hydrate is divided the Erlenmeyer flask injecting 200mL capacity, with autoclave 120 DEG C of vapor sterilizations 20 minutes.It is inoculated to the Gluconacetobacter xylinus (NBRC16670) grown in developmental tube slant agar substratum of 1 transfering loop, 30 DEG C of quiescent culture 7 days.After 7 days, generate the membranaceous bacteria cellulose of white gels on the upper strata of nutrient solution.
Embodiment 8
Use the bacteria cellulose obtained in Production Example 1 as cellulosic fibre.With mixing tank by after bacteria cellulose fragmentation, with water retting, repetitive scrubbing, carry out water displacement thus.Aqueous dispersions (being the aqueous dispersions of the bacteria cellulose of 60nm containing 4.1 quality % fiber diameter) 31 mass parts, ε-caprolactam 216 mass parts, hexosamine 44 mass parts, phosphorous acid 0.5 mass parts and Purified Water 50 mass parts of the bacteria cellulose after being replaced by water with mixing tank stir, are mixed to and become uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 240 DEG C in the way of heating, stir 1 hour at 240 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Embodiment 9
Aqueous dispersions (being the aqueous dispersions of the bacteria cellulose of 60nm containing 6.5 quality % fiber diameter) 35 mass parts, ε-caprolactam 194 mass parts, hexosamine 40 mass parts, phosphorous acid 0.5 mass parts and Purified Water 90 mass parts of the bacteria cellulose after being replaced by the water obtained similarly to Example 8 with mixing tank stir, are mixed to and become uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 240 DEG C in the way of heating, stir 1 hour at 240 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Utilize cryoultramicrotome from the test film obtained, cut the section that thickness is 100nm, use OsO
4after implementing section statining, carry out transmission electron microscope (NEC Inc. JEM-1230) and observe, the electron micrograph obtained in the cross section of shooting resin combination is shown in Fig. 1.
Embodiment 10
Aqueous dispersions (being the aqueous dispersions of the bacteria cellulose of 60nm containing 4.1 quality % fiber diameter) 71 mass parts, ε-caprolactam 162 mass parts, hexosamine 33 mass parts, phosphorous acid 0.38 mass parts and Purified Water 20 mass parts of the bacteria cellulose after being replaced by the water obtained similarly to Example 8 with mixing tank stir, are mixed to and become uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 240 DEG C in the way of heating, stir 1 hour at 240 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Embodiment 11
Add Purified Water in the aggregation of the cellulosic fibre produced as broken silk in the manufacturing process of non-woven fabrics, and utilize mixing tank to stir, preparation is the aqueous dispersions of the cellulosic fibre of 120nm containing 3 quality % fiber diameter.
With mixing tank, aqueous dispersions 170 mass parts of this cellulosic fibre, ε-caprolactam 216 mass parts, hexosamine 44 mass parts and phosphorous acid 0.59 mass parts are stirred, are mixed to and become uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 240 DEG C in the way of heating, stir 1 hour at 240 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Embodiment 12
Use identical with embodiment 11 aqueous dispersions containing 3 quality % cellulosic fibres, aqueous dispersions 85 mass parts of this cellulosic fibre, ε-caprolactam 216 mass parts, hexosamine 44 mass parts and phosphorous acid 0.59 mass parts are stirred with mixing tank, is mixed to and becomes uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 240 DEG C in the way of heating, stir 1 hour at 240 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Production Example 2: the cellulosic manufacture of miniaturization
Mierocrystalline cellulose (qualitative filter paper No.1) 2g is dispersed in and is dissolved with in the water 100mL of 2,2,6, the 6-tetramethyl--1-pyridines-N-oxyradical (TEMPO) of 0.025g and the Sodium Bromide of 0.25g.Then, adding 13 % by weight aqueous sodium hypochlorite solutions and making relative to the slurry of 1g, the amount of clorox is 4.3mmol.Adding aqueous sodium hydroxide solution to make the pH utilizing pH sat method to detect is after 10.5, pH does not change, stopped reaction.Adopt centrifugal separation to wash content with water 4 times, utilize home-use mixing tank to carry out solution fine 30 minutes.The fiber diameter of the cellulosic fibre obtained is 110nm.
Embodiment 13
Use the aqueous dispersions of the cellulosic fibre obtained in Production Example 2 containing 1.6 quality %, aqueous dispersions 95 mass parts of this cellulosic fibre, ε-caprolactam 131 mass parts, hexosamine 26 mass parts and phosphorous acid 0.3 mass parts carried out stir with mixing tank, be mixed to and become uniform dispersion liquid.Then, heat this mixed dispersion liquid lentamente, while discharge water vapor edge height temperature to 240 DEG C in the way of heating, stir 1 hour at 240 DEG C, carry out polyreaction.Take out the resin combination obtained at the time point be polymerized, cut off and make particle.With the particle that the hot-water cure of 95 DEG C obtain, carry out refining, make it dry.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Embodiment 14
Add Purified Water in the aggregation of the cellulosic fibre produced as broken silk in the manufacturing process of non-woven fabrics and utilize mixing tank to stir, preparation is the aqueous dispersions of the cellulosic fibre of 3240nm containing 6 quality % fiber diameter.
Use the aqueous dispersions of this cellulosic fibre, in addition, carry out polyreaction similarly to Example 11, obtain particle.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Embodiment 15
Use the aqueous dispersions containing 6 quality % cellulosic fibres identical with embodiment 14, in addition, carry out polyreaction similarly to Example 3, obtain particle.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 3.
Embodiment 16
Add Purified Water in the aggregation of the cellulosic fibre produced as broken silk in the manufacturing process of non-woven fabrics and utilize mixing tank to stir, preparation is the aqueous dispersions of the cellulosic fibre of 3240nm containing 2.6 quality % fiber diameter.
Use the aqueous dispersions of this cellulosic fibre, in addition, carry out polyreaction similarly to Example 4, obtain particle.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 4.
Embodiment 17
Use the aqueous dispersions containing 6 quality % cellulosic fibres identical with embodiment 14, in addition, carry out polyreaction similarly to Example 5, obtain particle.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 5.
Comparative example 1
Except not adding the aqueous dispersions of cellulosic fibre, carry out similarly to Example 1, thus obtain Amilan polyamide resin composition.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Comparative example 2
Except not adding the aqueous dispersions of cellulosic fibre, carry out similarly to Example 3, thus obtain Amilan polyamide resin composition.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 3.
Comparative example 3
Except not adding the aqueous dispersions of cellulosic fibre, carry out similarly to Example 4, thus obtain Amilan polyamide resin composition.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 4.
Comparative example 4
Except not adding the aqueous dispersions of cellulosic fibre, carry out similarly to Example 5, thus obtain Amilan polyamide resin composition.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 5.
Comparative example 5
Use the staple fibre (fiber diameter 16 μm) of cotton as cellulosic fibre, in addition, carry out similarly to Example 1, thus obtain Amilan polyamide resin composition.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Comparative example 6
Use the staple fibre (fiber diameter 16 μm) of the cotton identical with comparative example 5 as cellulosic fibre, in addition, carry out similarly to Example 3, thus obtain Amilan polyamide resin composition.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 3.
Comparative example 7
Use the staple fibre (fiber diameter 16 μm) of the cotton identical with comparative example 5 as cellulosic fibre, in addition, carry out similarly to Example 4, thus obtain Amilan polyamide resin composition.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 4.
Comparative example 8
Use the staple fibre (fiber diameter 16 μm) of the cotton identical with comparative example 5 as cellulosic fibre, in addition, carry out similarly to Example 5, thus obtain Amilan polyamide resin composition.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 5.
Comparative example 9
By the quantitative change of the aqueous dispersions of cellulosic fibre more 588 mass parts, in addition, carry out polyreaction similarly to Example 6, result cannot stir, and is difficult to polymerization.
Comparative example 10
As cellulosic fibre, use by after CELISH KY100G (Daicel Finechem Inc.: be the cellulosic fibre of 125nm containing 10 quality % fiber diameter) lyophilize, implement pulverization process and make the cellulosic fibre that powdery cellulose obtains.
Relative to nylon 6 (Unitika Corp BRL number-average molecular weight 17000) 100 mass parts, mix powdery cellulose 2 mass parts obtained, be supplied to the biaxial extruder (Chi Bei Inc. PCM-30) that screw diameter is 30mm, average channel depth is 2.5mm, with barrel temperature be 240 DEG C, screw speed is 120rpm, to be detained hour be that the condition of 2.7 minutes carries out melting mixing.Take out the resin combination obtained by melting mixing, cut off and make particle.By the particle straight forming obtained, carry out various physical property measurement.Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is identical with embodiment 1.
Carry out similarly to Example 9, the electron micrograph obtained in the cross section of the resin combination obtained in shooting comparative example 10 is shown in Fig. 2.Now, the test film obtained in comparative example 10 is by the visual scattered condensation product seeing a few mm.Fig. 2 is the photo obtained the part shooting cross section that cannot confirm condensation product by visual.
Comparative example 11
Use nylon66 fiber (Unitika Corp MALANIL A125 number-average molecular weight 18000) to replace nylon 6, in addition, carry out melting mixing equally with comparative example 10, acquisition resin combination, makes particle.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is barrel temperature is 270 DEG C, die temperature is 80 DEG C.
Comparative example 12
Use nylon 11 (Arkema company RILSAN BMN number-average molecular weight 15000) to replace nylon 6, in addition, carry out melting mixing in the same manner as comparative example 10, obtain resin combination, make particle.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is barrel temperature is 210 DEG C, die temperature is 80 DEG C.
Comparative example 13
Use nylon 12 (Arkema company RILSAN AMN number-average molecular weight 15000) to replace nylon 6, in addition, carry out melting mixing in the same manner as comparative example 10, obtain resin combination, make particle.
Should illustrate, injection molding condition when obtaining the test film used in flexural strength etc. measures is barrel temperature is 200 DEG C, die temperature is 80 DEG C.
The result of the characteristic value measuring the Amilan polyamide resin composition obtained in embodiment 1 ~ 17, comparative example 1 ~ 13 is shown in table 1.
[table 1]
Can be clear and definite by table 1, the Amilan polyamide resin composition obtained in embodiment 1 ~ 17 by by Fibre diameter be less than 10 μm cellulosic fibre aqueous dispersions with form the monomer of polyamide resin and mix and carry out polyreaction and obtain, therefore, fine in polyamide resin cellulosic fibre does not condense and disperses equably.Such dispersion state can be clear and definite by Fig. 1.That is, Fig. 1 is the cross section of Amilan polyamide resin composition obtained in shooting embodiment 9 and the electron micrograph obtained, and as shown in the region that it is surrounded by ellipse, cellulosic fibre does not condense each other but disperses.
Therefore, the Amilan polyamide resin composition obtained in embodiment 1 ~ 17, bending elastic modulus, modulus in tension, flexural strength, tensile yield strength are all high and the linear expansivity in MD direction is low, mechanical characteristics is excellent.And heat-drawn wire is high, thermotolerance is also excellent.
On the other hand, the Amilan polyamide resin composition obtained in comparative example 1 ~ 4, owing to not containing cellulosic fibre, therefore, compared with the Amilan polyamide resin composition of embodiment 1 ~ 5, bending elastic modulus, flexural strength, modulus in tension, tensile yield strength, heat-drawn wire are all low, and linear expansivity demonstrates high value, and mechanical characteristics, thermotolerance are all poor.The Amilan polyamide resin composition obtained in comparative example 5 ~ 8 adopts the cellulosic fibre of Fibre diameter more than 10 μm to carry out polyreaction, the Amilan polyamide resin composition obtained contains the cellulosic fibre of fiber diameter more than 10 μm, therefore, compared with the Amilan polyamide resin composition of embodiment 1 ~ 5, bending elastic modulus, flexural strength, modulus in tension, tensile yield strength, heat-drawn wire are all low, linear expansivity demonstrates high value, and mechanical characteristics, thermotolerance are all poor.In comparative example 9, the content of cellulosic fibre is too much, therefore, is difficult to stir, thus can not obtains resin combination when polyreaction.The Amilan polyamide resin composition obtained in comparative example 10 ~ 13 adopts the melting mixing method of manufacturing process not of the present invention to obtain, and therefore, in melting mixing operation, the dispersiveness of cellulosic fibre is very poor, and cellulosic fibre cohesion occurs.By the visual part that cannot confirm condensation product, this state is also the state that cellulosic fibre cohesion occurs in resin combination, such as, the cross section of resin combination obtained in shooting comparative example 10 and in the electron micrograph of Fig. 2 that obtains, demonstrating left and the condensation product of the cellulosic fibre of Bai You great from photo central part.Therefore, the Amilan polyamide resin composition obtained in comparative example 10 ~ 13 contains the large cellulosic fibre of fiber diameter, compared with the resin combination obtained in embodiment 1 ~ 5 (cellulosic fibre containing equivalent), bending elastic modulus, flexural strength, modulus in tension, tensile yield strength, heat-drawn wire are all low, linear expansivity demonstrates high value, and mechanical characteristics, thermotolerance are all poor.
Claims (10)
1. an Amilan polyamide resin composition, it is characterized in that, relative to polyamide resin 100 mass parts, containing cellulosic fibre 0.01 ~ 50 mass parts that fiber diameter is less than 10 μm, this Amilan polyamide resin composition by be less than 10 μm in fiber diameter and under the existence of the cellulosic fibre of state containing water, the polyreaction of monomer of carrying out forming polyamide resin obtains.
2. Amilan polyamide resin composition according to claim 1, wherein, heat-drawn wire during load 1.8MPa is more than 50 DEG C.
3. Amilan polyamide resin composition according to claim 1, wherein,
The linear expansivity in MD direction is 120 × 10
-6below, the linear expansivity in described MD direction calculates the mean value in 20 ~ 150 DEG C of regions and obtains, and its unit is 1/ DEG C.
4. Amilan polyamide resin composition according to claim 1, wherein,
Heat-drawn wire during load 1.8MPa is more than 50 DEG C, and the linear expansivity in MD direction is 120 × 10
-6below, the linear expansivity in described MD direction calculates the mean value in 20 ~ 150 DEG C of regions and obtains, and its unit is 1/ DEG C.
5. Amilan polyamide resin composition according to claim 1, wherein, heat-drawn wire during load 1.8MPa is more than 65 DEG C.
6. Amilan polyamide resin composition according to claim 1, wherein,
The linear expansivity in MD direction is 80 × 10
-6below, the linear expansivity in described MD direction calculates the mean value in 20 ~ 150 DEG C of regions and obtains, and its unit is 1/ DEG C.
7. Amilan polyamide resin composition according to claim 1, wherein,
Heat-drawn wire during load 1.8MPa is more than 65 DEG C, and the linear expansivity in MD direction is 80 × 10
-6below, the linear expansivity in described MD direction calculates the mean value in 20 ~ 150 DEG C of regions and obtains, and its unit is 1/ DEG C.
8. the Amilan polyamide resin composition according to any one of Claims 1 to 4, wherein, polyamide resin is nylon 11 or nylon 12.
9. the Amilan polyamide resin composition according to any one of claim 1,5 ~ 7, wherein, polyamide resin is nylon 6 or nylon66 fiber.
10. the manufacturing process of an Amilan polyamide resin composition, it is the method for the manufacture of the Amilan polyamide resin composition according to any one of claim 1 ~ 9, it is characterized in that, under fiber diameter is less than 10 μm and contains the existence of the cellulosic fibre of the state of water, carry out the polyreaction of the monomer forming polyamide resin.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-088164 | 2010-04-06 | ||
| JP2010088164 | 2010-04-06 | ||
| JP2010217104 | 2010-09-28 | ||
| JP2010-217104 | 2010-09-28 | ||
| JP2011-034598 | 2011-02-21 | ||
| JP2011034598 | 2011-02-21 | ||
| PCT/JP2011/058678 WO2011126038A1 (en) | 2010-04-06 | 2011-04-06 | Polyamide resin composition and method for producing polyamide resin composition |
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| Publication Number | Publication Date |
|---|---|
| CN102803385A CN102803385A (en) | 2012-11-28 |
| CN102803385B true CN102803385B (en) | 2015-07-22 |
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| CN201180014366.9A Active CN102803385B (en) | 2010-04-06 | 2011-04-06 | Polyamide resin composition and method for producing polyamide resin composition |
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| EP4053187A4 (en) * | 2019-10-30 | 2022-12-14 | Unitika Ltd. | Polyamide resin composition and molded article comprising same |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2557124A4 (en) | 2014-06-25 |
| KR101812986B1 (en) | 2017-12-28 |
| CN102803385A (en) | 2012-11-28 |
| CA2795068C (en) | 2018-08-21 |
| JP5885658B2 (en) | 2016-03-15 |
| EP2557124A1 (en) | 2013-02-13 |
| US8883885B2 (en) | 2014-11-11 |
| EP2557124B1 (en) | 2018-06-06 |
| CA2795068A1 (en) | 2011-10-13 |
| KR20130024885A (en) | 2013-03-08 |
| WO2011126038A1 (en) | 2011-10-13 |
| US20130030090A1 (en) | 2013-01-31 |
| JPWO2011126038A1 (en) | 2013-07-11 |
| HK1177946A1 (en) | 2013-08-30 |
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